Deviation In Isentropic Compressibility Research Articles

Application of PC‐SAFT EoS and SCFT for the modeling of thermophysical properties comprising deep eutectic solvent and alcohols

AbstractZinc (II) chloride based deep eutectic solvent (DES) were formed by mixing zinc (II) chloride with phosphoric acid. Fourier‐transform infrared spectroscopy was used to identify any possible shifts when the two compounds were assorted, and differential scanning calorimetry (SDT Q600 V20.9 Build 2D) was utilized to evaluate the formation of deep eutectic solvent. Densities, , and speed of sound, u, of [ZnCl2][phosphoric acid] 1:2.5 with methanol, ethanol, or propanol have been measured at T = (293.15, 303.15, 308.15, and 313.15) K and at atmospheric pressure. Excess molar volumes (), isentropic compressibilities (), deviation in isentropic compressibility (), and intermolecular free length () were calculated from the densities, and speed of sound, respectively. To fit the excess molar volumes and deviation in isentropic compressibilities, the Redlich–Kister smoothing polynomial was used. Also, we have used perturbed chain statistical associating fluid theory equation of state (PC‐SAFT EoS) for modeling the densities of the binary mixtures, and Schaaff's collision factor theory (SCFT) and Nomoto's relation (NR) were used for modeling the speed of sounds for the binary mixtures.

Thermodynamic properties of P-methyl acetophenone with cyclohexylamine, cyclohexanol, and cyclohexane at various temperatures (strong and weak interactions)

ABSTRACT The density, viscosity and sound velocity of the binary liquid mixtures of P-methyl acetophenone with cyclohexylamine, cyclohexanol, and cyclohexane are measured over the complete composition range at temperatures of 303.15–313.15 K and at atmospheric pressure of 0.1 M. Excess molar volume, excess isentropic compressibility and viscosity deviation are calculated from the experimental measurements. The sign and magnitude of the derived parameters reveal the nature and type of interactions between the constituent molecules in the binary mixtures. Thermodynamic properties for this work reveal association interactions between dissimilar molecules in the binary systems P-methyl acetophenone + cyclohexylamine and P-methyl acetophenone + cyclohexanol systems, whereas dispersion forces cause the opposite trend in the other binary system P-methyl acetophenone + cyclohexane.

Excess Properties, Partial Volume per Mole and FITR Spectral Studies in Liquid Mixtures of Furfuryl Alcohol with Primary and Secondary Anilines

ABSTRACT Speeds of ultrasound and densities of Furfuryl alcohol (FFA), Aniline (AN), N-Methylaniline (NMA) and N-Ethylaniline (NEA) along with the binary mixtures FFA+AN, FFA+NMA, FFA+NEA are measured at temperatures (303.15–318.15) K. From the experimental speed of ultrasound and density, excess parameters namely excess intermolecular free length ( L f E ), excess volume per mole ( V m E ) and deviation in isentropic compressibility (∆κs) are determined. The result of excess properties is supported by excess partial volume per mole ( V ˉ m , i E ) studies. The calculated excess and deviation functions have been fitted to the Redlich-Kister polynomial equation, and the observations have been analysed in terms of molecular associations. The variation of these excess parameters indicated the presence of specific interactions between component molecules. Further, FTIR spectra for the three mixtures were recorded and analysed to correlate with the thermodynamic and volumetric results. A good agreement was found between the two studies.

Molecular interactions between 2-methyltetrahydrofuran and alcohols: A combination of thermodynamic, spectroscopic and quantum chemistry studies

New data of density (ρ), viscosity (η), and speed of sound (u) have been determined at T = (288.15–303.15 K) and p = 93.2 kPa for the binary mixture of {2-methyltetrahydrofuran + ethanol, or + 1-propanol, or + 1-butanol, or + 1-pentanol} over the entire composition range. These results were used to calculate the excess molar volume (VmE), isentropic compressibility deviation (Δκs), viscosity deviation (Δη), and Gibbs excess activation energy (ΔG*E), which were correlated by a Redlich-Kister polynomial. For all systems studied, the values ​​of the deviation properties were negative, which probably indicates a predominance of structural and chemical effects over physical effects. Five viscosity models were employed to fit the viscosity data. The VmE data were also correlated by the Prigogine-Flory-Patterson Theory (PFP Theory) and the Peng-Robinson-Stryjek-Vera Equation of State (PRSV EOS). Furthermore, a Fourier Transform Infrared (FT-IR) spectroscopy study was performed to explain the hydrogen bonding interactions. Lastly, theoretical calculations using Density Functional Theory (DFT) at B3LYP-GD3(BJ)/6–311++G(3df,2p) level of theory were performed to understand the inter-interactions between the compounds present in the mixtures. The FT-IR and computational results were in good agreement with the experimental data.

Application of ERAS-model and PFP theory on excess and deviation properties for binary systems of ionic liquid + amine derivatives

Thermodynamics of mixtures includes ionic liquid 2-hydroxyethylammonium propionate [2-HEAPr] + 1-propanol, 3-amino-1-propanol [AP], 1-amino-2-propanol [MIPA], and monoethanolamine [MEA] were studied. Density ρ, speed of sound u, and refractive index nD of pure and mixtures were measured at T = (298.15, 308.15, 318.15) K. Excess molar volume VmE, excess partial molar volume Vm,iE, excess thermal expansion coefficient αE, isothermal coefficient of excess molar enthalpy (∂Hm∂P)T,x, deviations in isentropic compressibility Δ ks, and refractive index Δ nD were calculated and data correlated with Redlich-Kister polynomial relation. The Prigogine-Flory-Patterson (PFP) and Extended Real Associated Solution (ERAS) models were applied to analyze intramolecular and intermolecular interactions between like and unlike molecules. The accuracy of theoretical models were found to be in agreement with empirical results. Finally, the study confirmed the structures of the ILs using FT-IR and HNMR analysis.

Thermodynamic study of mesitylene + alkanol mixtures: Insights into molecular interactions

Excess properties are a powerful tool for understanding the intermolecular interactions in mixtures. In this study, the excess molar volume (VmE), excess isentropic compressibility (κsE) deviation in ultrasonic speed (Δu), and refractive index (ΔnD) were analyzed for mixtures of mesitylene and alkanol to interpret their intermolecular interactions. Our findings demonstrate that positive values of VmE and κsE indicate the predominance of the rupture of H-bonding in self-associated alkanol dominate over the electron donor–acceptor interaction between the hydroxyl group of alkanol and π–electrons of mesitylene. It was also observed that these electron donor–acceptor interactions weaken as the temperature increases. These observations were further supported by the behavior of molecular association parameter (MA), free intermolecular length, and available volume. Among the alkanols studied, n-butanol exhibited the highest value of MA, suggesting a strong degree of molecular association due to favorable intermolecular interactions between the dissimilar molecules. In contrast, sec-butanol showed the lowest value, which can be attributed to the steric hindrance caused by three methyl groups of mesitylene and the two methyl groups attached to a hydroxyl carbon atom in sec-butanol. Regarding correlation, Schaffs collision factor theory demonstrated high predictive power for ultrasonic speed compared to other models.

Thermodynamic study of triacetin or ethyl levulinate and alcohol binary mixtures

The subject of presented research is the study of liquid binary mixtures consisting of ester and alcohol combination; triacetin or ethyl levulinate, as one component, and ethanol or isobutanol, as second component. Thermodynamic and transport data were measured in the broad temperature range, T=(288.15/298.15–323.15/333.15) K, and at atmospheric pressure, p = 0.1 MPa. All corresponding excess and deviation properties were calculated including the excess molar volume, viscosity deviation, refractive index deviation, isentropic compressibility deviation and excess molar Gibbs energy of activation of viscous flow, and correlated with the basic Redlich-Kister equation. The analysis of possible chemical interactions and structural effects taking place in the mixtures was led in the terms of ester structure, complexity of ester molecule and chain length and branching of the alcohol molecule. The thermodynamic analyses showed change of the sign of the excess molar volume depending on the alcohol present in the mixture. FT-IR spectra were recorded for all four systems for the compositions where maximum excess molar volumes are obtained to support the conclusions derived from the mixtures’ nonideal behaviour. In addition, modelling of viscosity is performed with the two- and three-parameter correlative models, as well as excess molar volume correlation with the Peng-Robinson equation of state and three-parameter van der Waals mixing rule.

Volumetric properties of binary liquid mixture of cyclopentyl methyl ether with 1-pentanol at 298.15 k temperature

The densities (ρ) and ultrasonic speeds (u) of Cyclopentyl methyl ether, 1- Pentanol and their binary mixture with the whole composition range have been measured at 298.15 K. From the experimental data the excess molar volume (VE), deviations in isentropic compressibility (∆ks), deviations in ultrasonic speed (∆u), deviations in acoustic impedance (∆Z) have been determined. The sign and magnitude of these parameters were found to be sensitive towards interactions prevailing in the studied system. Moreover, VE values were theoretically predicted by using Flory’s statistical theory. The variations of derived parameters mentioned above with composition offer a convenient method to study the nature and extent of interactions between the component molecules of the liquid mixture not easily obtained by other means.

Thermodynamic properties of binary liquid mixtures of benzyl alcohol with 2-Alkoxyethanols at varying temperatures

In the present research, density (ρ) and speed of sound (u) for binary liquid mixtures of the benzyl alcohol (BA) with three 2-alkoxyalcohols {2-methoxyethanol (2-ME), 2-ethoxyethanol (2-EE), and 2-butoxyethanol (2-BE)} at temperatures of 298.15, 303,15 and 308.15 K have been measured over complete concentration of benzyl alcohol under 0.1 MPa pressure. According to measured results, excess molar volume (VmE) and deviation in isentropic compressibility (Δκs) were computed and these observed results were correlated to Redlich−Kister (R-K) polynomial expansion. Further, molar volume (Vm), apparent molar volumes (Vm,∅,1 and Vm,∅,2), acoustic impedance (Z), isentropic compressibility (ks), intermolecular free length (Lf), deviation in intermolecular free length (ΔLf) were calculated at all worked temperatures. For all studied systems, excess molar volume (VmE) and deviation in isentropic compressibility (Δκs), and deviation in intermolecular free length (ΔLf) were negative over the entire mole fraction range of benzyl alcohol at all measured temperatures. Among the three systems, benzyl alcohol with 2-ethoxyethanol containing system showed more negative. By using the obtained results, intermolecular interactions were discussed between benzyl alcohol and 2-alkoxyethanols. Moreover, the influence of temperature on intermolecular interactions was analyzed using above said parameters.

Thermodynamic Properties of Binary Liquid Mixtures Containing Furfural with Chlorobenzene, Nitromethane, Diethylmalonate and 1-Butanol at 308.15K and 318.15K Supported by FTIR Spectral Studies

A study on thermodynamic properties of the liquid mixture is used in the industrial process, which often extends to solution chemistry. Density(ρ), Viscosity(η), and Ultrasonic velocity(U) were determined for binary liquid mixtures of furfural with chlorobenzene, nitromethane, diethyl malonate and 1- butanol at temperature of 308.15K and 318.15K at atmospheric pressure over the whole range of mole fractions. The calculated thermodynamic properties and some excess parameters such as Excess Volume(VE), Deviation in Isentropic Compressibility(∆KS), Deviation in Viscosity(∆η), Deviation in Intermolecular Free Length(∆LF), Deviation in Intermolecular Free Volume(∆VF), Deviation in Internal Pressure(∆π) and Deviation in Acoustic Impedance(∆Z) were calculated and applied to the Redlich-Kister type polynomial equation to determine the appropriate coefficients. The effects of composition and temperature on thermodynamic parameters have been studied in terms of molecule interaction in these liquid mixtures. Further, IR spectra of these liquid mixtures were recorded and the data were utilized to examine the mixing behavior of the components.

Molecular interactions of (ionic liquid butylammonium methanoate + alcohols) at several temperatures. Part II: sec-Butylammonium methanoate (S4Met)

Volumetric and acoustic properties were obtained by density (ρ) and speed of sound (u) experimental values for the binary liquid systems containing the protic ionic liquid (IL) sec-butylammonium methanoate (S4Met) + alcohols (ethanol, 1-propanol, 1-butanol and 1-pentanol) over the whole composition range at different temperatures (293.15–313.15) K and ambient pressure (p = 92.3 kPa). A neutralization reaction was carried out under controlled temperature to synthesize S4Met, which underwent spectroscopic analyses to guarantee its formation. All the excess properties, namely excess molar volume,VmE, excess partial molar volumes,V¯iE, and deviation in isentropic compressibility,ΔκS, presented negative values. Other volumetric properties such as partial molar volumes,V¯i, apparent molar volumes, Vϕi and infinite dilution volumes,V¯i∞, were determined. In addition to the thermodynamic approach, spectroscopy techniques essentially 1H NMR, 13C NMR, FTIR were useful in order to elucidate intermolecular interactions among the species in solutions. Lastly, the Peng-Robinson-Stryjek-Vera equation of state (PRSV EOS) was used to correlate the excess molar volumes.

The mixing properties, IR analysis and quantum chemical calculations of trimethoxylsilane derivatives with ethanol, 1-butanol, 1-pentanol and 1-octanol

The density, viscosity and speed of sound of trimethoxylsilane derivatives with ethanol, 1-butanol, 1-pentanol and 1-octanol have been measured at 298.15, 303.15, 308.15, 313.15 K, 318.15 and 323.15 K, respectively. The excess molar volume, viscosity deviation, excess Gibbs energy of activation of viscous flow, isobaric thermal expansivity and isentropic compressibility deviation were calculated from these results. The Redlich–Kister equation was used for the correlation. The calculated excess properties have been discussed according to the possible interactions formed between the molecules in the mixture using equimolar attenuated total reflection Fourier transform infrared (ATR-FTIR) spectroscopy. In all of the compositions and experimental temperature ranges studied, the excess molar volumes were found to be negative for vinyl trimethoxy silane and phenyl trimethoxy silane with ethanol. This may be attributed to the close accumulation of molecules and easier formation of cross-association structures between the alkoxysilane molecules. However, the excess molar volume of the binary mixture of vinyl trimethoxy silane and phenyl trimethoxy silane with n-butanol, n-pentanol, and n-octanol was positive. Hydrogen bond fracture may play a leading role in this process. The excess molar volumes of the binary system comprised of trifluoropropyl trimethoxy silane with ethanol and 1-octanol were all positive. This may be attributed to the influence of steric hindrance, which makes it difficult for trifluoropropyl trimethoxy silane to form a cross-association structure with alcohol molecules.

Influence of water and ethanol in the physical properties of choline glycinate at several temperatures

In this study, a physical characterization (density (ρ), refractive index (nD), speed of sound (u) and dynamic viscosity (η)) as a function of temperature (298.15–343.15 K) of choline glycinate (ChGly) and its binary mixtures with water or/and methanol over the entire composition range was performed from 298.15 K to 323.15 K. Several derived properties of the pure ionic liquid and excess molar volume (VmE) changes of refractive index on mixing (ΔnD), deviations in isentropic compressibility (ΔκS) and viscosity deviations (Δη) have been calculated using the experimental data in the selected temperature range. These experimental data of ChGly have been positively correlated using polynomial equations and the derived magnitudes were successfully fitted to Redlich-Kister equation. Finally, different models have been implemented for the first time to predict the density of the selected binary mixtures as a function of the temperature.

Densities and Sound Speeds of Ternary Mixtures Methyl tert-Butyl Ether + Toluene + n-Hexane (or Cyclohexane) and Their Binary Subsystems at a Temperature of 298.15 K and under Ambient Pressure

Densities ρ and sound speeds c of the ternary systems methyl tert-butyl ether (MTBE) + toluene + n-hexane, MTBE + toluene + cyclohexane, and related binary subsystems MTBE + toluene, MTBE + n-hexane, toluene + n-hexane, MTBE + cyclohexane, and toluene + cyclohexane are measured over the whole composition range at 298.15 K and under ambient pressure. The excess molar volumes, VmE, and isentropic compressibility deviations, ΔκS, were derived from experimental ρ and c data. The experimental results are discussed in terms of the possible interactions between molecules in the mixture and structural effects. The VmE and ΔκS data for the binary and ternary systems were correlated with the Redlich–Kister and Cibulka equations, respectively. Further, the ternary VmE and ΔκS data are compared with the predicted values using the binary contribution models of Radojković, Kohler, Rastogi, Tsao-Smith, Toop, and Scatchard. The root-mean-squared deviation between experimental and predicted values is used as a tool to measure the predicting capabilities of the tested models.

Volumetric, acoustic and viscometric properties of binary mixtures containing acetonitrile with glycols at several temperatures: Experimental study and correlations

Density, speed of sound and viscosity of binary mixtures of {acetonitrile + ethylene glycol (EG), or + diethylene glycol (DEG), or + triethylene glycol (TEG)} have been measured as a function of compositions at temperatures of 288.15, 293.15, 298.15 and 303.15 K and under atmospheric pressure. Excess molar volume, partial molar volume, excess partial molar volume, deviation in isentropic compressibility and deviation in viscosity were determined and excess properties have been fitted to the Redlich-Kister equation. The empirical models developed by Grünberg-Nissan, Heric-Brewer, Katti-Chaudhary and Van der Wyk were used to correlate the experimental viscosity data. The excess molar volume was also used to test the applicability of the Peng-Robinson-Stryjek-Vera equation of state (PRSV EOS).

A study on mixing properties of binary mixtures of 1-hexene with alkoxyethanols at different temperatures

Blends of 1-hexene with alkoxyethanols have been studied in terms of intermolecular interactions. The investigated alkoxyethanols were 2-methoxyethanol or 2-ethoxyethanol or 2-butoxyethanol. This study was based on measurements of densities, ρ, speeds of sound, u, and refractive indices, nD, throughout the full range of composition. With the help of measured data, some derived/excess properties have been computed such as excess molar volume, VmE, isentropic compressibility,κs, deviation in isentropic compressibility, Δκs, and deviation in refractive indices, ΔnD and these properties were fitted to a Redlich−Kister equation. Furthermore, PC-SAFT equation of state (PC-SAFT EoS) were used to correctly modeled the density of pure fluids and mixtures whereas the Nomoto’s relation modeled the speed of sound for the binary mixtures with the least deviation, while for the refractive index of all the mixtures, Laplace mixing rule was the best approach..

Excess Thermodynamic Properties of Ethyl Acetate with Primary Alcohols At 303.15 K

Densities (ρ) and sound velocity (u) for the binary mixtures of ethyl acetate with 1-methanol, 1- ethanol, 1- propanol, 1- butanol, 1-hexanol and 1-octanol were measured over the entire composition range at 303.15 K. From these data, excess molar volume (VE), isentropic compressibility (Ks ) and deviation in isentropic compressibility (ΔKs ) have been calculated with the Redlich-Kister Polynomial equation. The experimental data were discussed in terms of intermolecular interactions between component molecules.

Density, speed of sound, refractive index of binary mixtures containing 2-ethoxyethanol and some alcohols: Measurement and correlation

The aim of this research to investigate thermophysical properties of alkoxyethanols with alcohols, including densities, speeds of sound, and refractive index of five binary mixtures constituted by 2-ethoxyethanol (2EE) + methanol, or ethanol, or propan-1-ol, or propan-2-ol, or butan-2-ol, that have been measured at the temperatures: (293.15, 303.15, 313.15 and 323.15) K, over the entire composition range and at pressure of p = 0.1 MPa. The Cubic Plus Association equation of state (CPA-EOS) has been used to correlate the measured properties. From the measured data, excess/derived properties: excess molar volume, isentropic compressibility, deviation in isentropic compressibility and deviation in refractive index were calculated and correlated using the Redlich − Kister equation. The results obtained from the work have been discussed in terms of the nature of molecular interactions between the components of the mixture.

Optimization of Thermo-Physical Properties For The Binary System Of Acetone–Water At 303.15-318.15 K By Response Surface Quadratic Model

Thermo bodily residences of binary liquid combos are very beneficial in biotechnology, pharmaceutical, chemical and petroleum refining industries for improved favoured products from diverse raw materials. The physical property data on mixed solvents are important for the theoretical and applied areas of research and are frequently used in many chemical and industrial processes such as design of new process and process equipment (fluid flow, mass transfer or heat transfer calculation) and designing of bioreactor/fermenter. The objective of the current paper is to determine the density, viscosity, ultrasonic velocity, refractive index and surface tension of acetone (1) + water (2) at temperatures of 303.15K to 318.15K for the complete composition degrees and atmospheric pressure. These experimental values were used to calculate the respective excess homes in conjunction with a few acoustic properties. The experimental facts and excess residences have been used to calculate the interacting coefficients and well known deviations from different existing models. Also the new model equations have been evolved with the aid of the use of Design Expert application for density, viscosity, ultrasonic velocity, refractive indices and surface tension. Experimental consequences have been analysed on the premise of molecular interactions among element molecules with the assistance of FT-IR spectrum. Acetone-water binary structures of the prevailing observer have positive values of excess molar volumes and deviations in isentropic compressibility over whole composition range and at all temperatures which suggests sturdy interactions among the components of binary mixtures. Thermodynamic observations of acetone and water mixtures were made. Negative viscosity deviation of acetone-water combinations suggests robust dipole-dipole interactions within the device. Fourier remodel infrared spectroscopy also indicates the sturdy interaction made at 3589 cm-1 and based on the response surface method outcomes, more interplay takes area at zero. Five and zero six moles of acetone and water combination and the consequences are conformed with reference to the R2 cost (0.89). Excess molar extent and isentropic compressibility were decided and kinds of interactions have been discussed primarily based on the derived properties.

Understanding of the interactions between azole-anion-based ionic liquids and 2-methyl-3-butyn-2-ol from the experimental perspective: the cage effect.

The interactions between azole-anion-based ionic liquids (AILs) and 2-methyl-3-butyn-2-ol (MBY) play an important role in AIL-promoted carboxylative cyclization of MBY with CO2. To better understand the interactions between AILs ([P66614][Im], [P66614][4-MeIm], and [P66614][4-BrIm]) and MBY, a detailed investigation from the experimental perspective has been carried out in this study. The results show that the derivative of viscosity (η) with the mole fraction of AIL (xAIL) of AIL + MBY mixtures appears to have the maximum value when xAIL ≈ 0.3, while 1H NMR chemical shifts of P-CH2 of [P66614]+ reach the minimum value at xAIL ≈ 0.3, indicating that [P66614]+ of AILs tend to self-aggregate. The interaction parameters (gji-gii) of the systems obtained from η by the Eyring-UNIQUAC equation are positive, and the difference between the bulk and local composition (xi-xii) is always negative, indicating that AILs can interact with MBY. Moreover, excess molar volumes and isentropic compressibility deviations are all negative deviations and become more negative as the temperature increases, reaching a minimum value at xAIL ≈ 0.30, indicating that azole-based anions can form H-bonds with MBY, and MBY molecules tend to enter the aggregates formed by AILs. Consequently, the cage effect is proposed to describe the interactions between AILs and MBY: MBY first enters the cage formed by the aggregation of [P66614]+, and then forms H-bonds with azole-based anions. Finally, the sizes of the particles of the [P66614][Im] + MBY mixture from dynamic light scattering increase first and then decrease with xAIL, with the maximum of 122 nm at xAIL ≈ 0.25, which confirms the rationality of the cage effect.